CN101151334A - Ink composition, recording method using the same, and recorded matter - Google Patents
Ink composition, recording method using the same, and recorded matter Download PDFInfo
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- CN101151334A CN101151334A CNA200680010248XA CN200680010248A CN101151334A CN 101151334 A CN101151334 A CN 101151334A CN A200680010248X A CNA200680010248X A CN A200680010248XA CN 200680010248 A CN200680010248 A CN 200680010248A CN 101151334 A CN101151334 A CN 101151334A
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Abstract
This invention provides an ink composition that can yield images having an excellent glossy impression on glossy recording media. The ink composition comprises at least a colorant coated with a water insoluble polymer and a resin emulsion and is characterized in that the water insoluble polymer has a weight average molecular weight of 50000 to 150000, the resin emulsion comprises a resin of a monomer component, which is the same type as the monomer component constituting the water insoluble polymer, and the resin has a weight average molecular weight of 1.5 to 4 times larger than the weight average molecular weight of the water insoluble polymer. Alternatively, the ink composition comprises at least a colorant coated with a water insoluble polymer and resin particles and is characterized in that the colorant coated with the water insoluble polymer is a coloring material prepared by a phase inversion emulsification method and the resin particles are formed of a polymer prepared by an emulsion polymerization method.
Description
Technical field
The present invention relates to a kind of ink composition.More particularly, relate to a kind of ink composition that is applicable to ink-jet recording.
Background technology
Ink-jet recording is that the small droplets of black liquid is circled in the air, and is attached on the recording mediums such as paper and the printing process of printing.Innovative progress along with in recent years ink-vapor recording technology, up to now, in the high meticulous image recording (printing) in the field that belongs to photo or offset printing, also use gradually and go up ink jet recording method, the dedicated paper of using for general used common paper or ink-vapor recording (asperities series, gloss series) not only, and also require high quality record for the recording mediums such as paper that are actually used in printing.
As black liquid used in the ink-vapor recording, in general known have comprise the ink composition that becomes the look of tinting material material, water, water-soluble organic compounds, tensio-active agent etc.
As tinting material, can use dyestuff or pigment, particularly for color ink liquid, consider from the reasons such as solvability height of the size of the chroma of color, the transparency, Xiang Shuizhong, use water-soluble dye more.But, this kind dyestuff in general photostabilization or anti-gaseousness aspect is abundant inadequately, in addition, owing to be water-soluble, therefore problem is also arranged aspect water tolerance, and utilization has used the record thing of the black liquid record of water-soluble dye to have the shortcoming of the keeping quality difference of document image.Different with it, water-fast tinting material is favourable aspect water tolerance.Particularly in the middle of the tinting material of water fast, pigment is owing to be good look material aspect such photostabilization, anti-gaseousness, water tolerance, therefore the exploitation for the pigment inks liquid that has utilized this look material characteristic advances, and for example proposes pigment with tensio-active agent or the dispersed water-based paint China ink of macromolecule dispersing agent liquid; Used the water-based paint China ink liquid of surface of pigments having been given the functional group that can carry out water-dispersion from dispersed color; With the water-based paint China ink liquid of pigment with the covered toner of resin that can carry out water-dispersion.
This kind pigment inks liquid is the material that has stably disperseed pigment particles (also comprising the toner that contains pigment) in black liquid, yet black liquid attached to recording mediums such as paper on after, in black liquid exsiccant process, be accompanied by the evaporation of moisture or volatile solvent based, stable dispersion is damaged, and causes the cohesion of pigment easily.When the pigment that has condensed is separated out on recording mediums such as paper, then can lose the smoothness on surface, make glossiness reduce or the homogeneity of printed images worsens, thereby the problem that can't obtain high-quality image arranged.In addition, because of the reflected light of the pigment of separating out, will observe the color (bronzing phenomenon) of the tone different, thereby the problem of the image of the required tone that can't obtain homogeneous is arranged with original tone.In addition, wiped to draw because of the pigment of separating out and peeled off, thereby aspect stationarity, problem is arranged also to the surface; Because of being scratched at pigment surperficial in contacts such as finger or wearing and tearing, reflecting feel changes, thus the problem of rub resistance aspects such as glossy sense change.
Picture quality for pigment inks liquid, for improving purposes such as glossiness or dispersiveness, proposed following scheme, that is, limit and to be scattered in the particle dia (with reference to patent documentation 1) of the pigment in the black liquid, to contain pigment and pigment derivative (with reference to patent documentation 2) simultaneously; Purpose for improving perviousness or color emissivity proposed following scheme, that is, contain polymer particles (with reference to patent documentation 3), contain inorganic particles (with reference to patent documentation 4); For the lettering concentration on the raising common paper and the purpose of the glossiness on the ink-jet dedicated paper, proposed to contain the black liquid (with reference to patent documentation 5) of the water-insoluble vinyl polymer dispersion that comprises pigment etc.
But in this kind pigment inks liquid, the homogeneity of glossiness or printed images is also abundant inadequately, particularly because of the reflected light of the pigment that condenses upon the paper surface, and the problem of the color (bronzing phenomenon) of observing the tone different with original tone is arranged; Or have aspect the rub resistance that changes and so at the stationarity of black liquid or gloss, for the ropy problem of water-soluble dye China ink liquid.
Patent documentation 1: the spy opens the 2002-356637 communique
Patent documentation 2: the spy opens the 2002-294134 communique
Patent documentation 3: the spy opens the 2001-123098 communique
Patent documentation 4: the spy opens flat 11-209671 communique
Patent documentation 5: the spy opens the 2005-41994 communique
Summary of the invention
The present invention finishes in view of described problem, its purpose is, a kind of ink composition is provided, be on various recording mediums, particularly have and do not have the bronzing phenomenon on the glossy recording medium, can obtain to have the ink composition of the image of good reflecting feel, its rub resistance is good, is specially adapted to ink-jet recording.
The inventor etc. further investigate, and the result has obtained following opinion, that is, the ink composition that contains by the covered tinting material of insoluble polymer, specific resinous principle can solve described problem.The present invention is based on the invention of this opinion.
First mode of the present invention relates to following ink composition, recording method and record thing.
(1) a kind of ink composition, be to contain at least as the tinting material that covers by insoluble polymer of look material with as the ink composition of the resin emulsion of additive, it is characterized in that, the weight-average molecular weight of insoluble polymer is 50000～150000, resin emulsion is the resin formation of 1.5 times～4 times weight-average molecular weight by forming with the monomer component that constitutes this insoluble polymer monomer component of the same race with respect to this insoluble polymer by its molecular weight.
(2) according to (1) described ink composition, it is characterized in that described tinting material is water-fast tinting material.
According to (1) or (2) described ink composition, it is characterized in that (3) polymkeric substance of described insoluble polymer and formation resin emulsion is the branched chain type polymkeric substance.
(4) according to any described ink composition in (1)～(3), it is characterized in that the median size of described resin emulsion is 20～200nm.
(5) according to any described ink composition in (1)～(4), it is characterized in that, described tinting material is a pigment, and described ink composition also contains water and water-soluble organic compounds, and the median size of the pigment particles in the ink composition is in the scope of 50～150nm.
(6) according to (5) described ink composition, it is characterized in that described water-soluble organic compounds is made of the butyl ethers of polyalcohols, solid wetting agent and glycol at least.
(7) according to (6) described ink composition, it is characterized in that, polyalcohols is by being selected from glycerine, glycol ether, triglycol, 1,5-pentanediol and 1, constituting more than 2 kinds in the 2-hexylene glycol, the solid wetting agent is trimethylolethane or TriMethylolPropane(TMP) or urea, and the butyl glycols is diglycol monotertiary butyl ether or triglycol single-butyl ether.
(8) according to any described ink composition in (1)～(7), it is characterized in that, be used in the ink-jet recording.
(9) a kind of recording method comprises any described ink composition in (1)～(8) is attached on the recording medium and carries out the operation of lettering.
(10) according to (9) described recording method, it is characterized in that, also comprise the operation of the drop that sprays black liquid, this drop is attached on the recording medium and carries out lettering.
(11) a kind of record thing is to utilize the recording method record described in (9) or (10).
Second mode of the present invention relates to following ink composition, recording method and record thing.
(12) a kind of ink composition, be to contain the tinting material that covers by insoluble polymer, the ink composition of resin particle at least, it is characterized in that, insoluble polymer is the polymkeric substance that uses polymerizability unsaturated monomer and polymerization starter to utilize solution polymerization process to obtain at least, the tinting material that is covered by insoluble polymer is to utilize the following look material that emulsion process obtains that changes mutually, promptly, after being dissolved in this insoluble polymer in the organic solvent, at least add tinting material and water mixes, remove organic solvent, be scattered in the aqueous systems; Resin particle is to use linking agent at least, the polymkeric substance that utilizes emulsion polymerization to obtain.
(13) according to (12) described ink composition, it is characterized in that described tinting material is water-fast tinting material.
(14) according to (12) or (13) described ink composition, it is characterized in that described insoluble polymer is the branched chain type polymkeric substance.
(15) according to any described ink composition in (12)～(14), it is characterized in that described resin particle is by not becoming the polymkeric substance of membranization to constitute under the temperature below 40 ℃.
(16) according to any described ink composition in (12)～(15), it is characterized in that the median size of described resin particle is 20～80nm.
(17) according to any described ink composition in (12)～(16), it is characterized in that described tinting material is a pigment, described ink composition also contains water and water-soluble organic compounds, and the median size in the ink composition is in the scope of 50～150nm.
(18) according to (17) described ink composition, it is characterized in that described water-soluble organic compounds is made of the butyl ethers of polyalcohols, solid wetting agent and glycol at least.
(19) according to (18) described ink composition, it is characterized in that, polyalcohols is by being selected from glycerine, glycol ether, triglycol, 1,5-pentanediol and 1, constituting more than 2 kinds in the 2-hexylene glycol, the solid wetting agent is trimethylolethane or TriMethylolPropane(TMP) or urea, and the butyl glycols is diethylene glycol monobutyl ether or triglycol monobutyl ether.
(20) according to any described ink composition in (12)～(19), it is characterized in that, be used in the ink-jet recording.
(21) a kind of recording method comprises any described ink composition in (12)～(20) is attached on the recording medium and carries out the operation of lettering.
(22) according to (21) described recording method, it is characterized in that, also comprise the operation of the drop that sprays black liquid, this drop is attached on the recording medium and carries out lettering.
(23) a kind of record thing is to utilize the recording method record described in (21) or (22).
Embodiment
To the ink composition based on first mode of the present invention preferred embodiment be described based on it below.
The ink composition of first mode of the present invention is to contain at least by the tinting material of insoluble polymer covering and the ink composition of resin emulsion, it is characterized in that, the weight-average molecular weight of insoluble polymer is 50000～150000, resin emulsion is the resin formation of 1.5～4 times weight-average molecular weight by forming with the monomer component that constitutes this insoluble polymer monomer component of the same race with respect to this insoluble polymer by its molecular weight.
These integrants are elaborated.
[look material]
Used look material is the tinting material that is covered by insoluble polymer at least in the ink composition of first mode of the present invention, used insoluble polymer is made of the monomeric copolymer resin of monomer with hydrophobicity base and possess hydrophilic property base in this look material, contains to have the residues of monomers that salt generates base at least.Here, so-called insoluble polymer is meant that the solubleness of neutralization back in 25 ℃ water 100g is less than the polymkeric substance of 1g.
Monomer with hydrophobicity base has: methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, the methacrylic acid cyclohexyl ester, the methacrylic acid phenylester, benzyl methacrylate, methyl acrylic esters such as methyl propenoic acid glycidyl base ester; Vinyl esters such as vinyl-acetic ester; Vinyl cyanide compound such as vinyl cyanide, methacrylonitrile class; Aromatic vinyl monomer classes such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl benzene methyl ether, vinyl naphthalene etc. can be distinguished separately and use, and perhaps also can mix more than 2 kinds and use.
As the monomer of possess hydrophilic property base, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene glycol propylene glycol monomethyl acrylate etc. are arranged, can distinguish separately and use, perhaps also can mix more than 2 kinds and use.Particularly, then can improve the glossiness of printed images by using the monomer component of formation side chains such as polyoxyethylene glycol (2～30) monomethacrylates, polyoxyethylene glycol (1～1 5) propylene glycol (1～15) monomethacrylates, polypropylene glycol (2～30) methacrylic ester, methoxy poly (ethylene glycol) (2～30) methacrylic ester, methoxyl group polytetramethylene glycol (2～30) methacrylic ester, methoxyl group (ethylene glycol propylene glycol copolymers) (1～30) methacrylic ester.
Monomer with salt generation base has vinylformic acid, methacrylic acid, vinylbenzene carboxylic acid, toxilic acid etc., can distinguish separately and use, and perhaps also can mix more than 2 kinds and use.
In addition, can and be used in macromonomer or other monomers such as the polystyrene macromonomer that has the polymerization functional group on the end, polysiloxane series macromonomer.
The insoluble polymer of first mode of the present invention can be by utilizing known polymerizations such as mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization, monomer copolymerization is obtained, yet special preferred solution polymerization, in polymerization, also can add known radical polymerization mixture or polymeric chain transfer agent.
The tinting material that is covered by insoluble polymer in first mode of the present invention for example can followingly obtain, promptly, described insoluble polymer is dissolved in the organic solvents such as methyl alcohol, ethanol, Virahol, propyl carbinol, acetone, methyl ethyl ketone, dibutyl ether, in the solution of gained, add tinting material, add the dispersion that neutralizing agent and water are mixing, dispersion treatment is adjusted oil droplet type in the water then, by from the dispersion of gained, removing organic solvent, and obtain as water dispersion.Mixing, dispersion treatment for example can be used ball mill, roller mill, ball mill, high-pressure homogenizer, high-speed stirring type dispersion machine etc.
Tertiary amine, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia etc. such as the preferred ethamine of neutralizing agent, Trimethylamine 99, the pH of the water dispersion of gained preferred 6～10.
In addition,, make tinting material as the insoluble polymer that covers, pigment dispersive aspect stably particularly, preferable weight-average molecular weight is about 50000～150000 polymkeric substance.Weight-average molecular weight can utilize the molecular weight analyse method of gel permeation chromatography (GPC) to measure.
As operable tinting material in the tinting material that covers by insoluble polymer of first mode of the present invention, can use existing dyestuff, the pigment put down in writing in " dyestuff handbook " (publisher: ball is apt to Co., Ltd.) etc.
The tinting material of the preferred water fast of tinting material of first mode of the present invention, preferred tinting material are pigment.As the pigment that can be used for first mode of the present invention, can use any kind of known mineral dye and pigment dyestuff, except pigment such as the middle Pigment Yellow 73 of putting down in writing of color table (color index), Pigment red, pigment violet, Pigment blue, Pigment black, can also pigment such as phthalocyanines, azo class, anthraquinone class, azomethine class, condensation lopps be shown example.In addition, can also enumerate yellow No. 4, No. 5, No. 205, No. 401; Orange No. 228, No. 405; Mineral dyes such as pigment dyestuff such as blue No. 1, No. 404, titanium oxide, zinc oxide, zirconium white, ferric oxide, ultramarine, Prussian blue, chromic oxide.For example, C.I. Pigment Yellow 73 1,3,12,13,14,17,24,34,35,37,42,53,55,74,81,95,97,98,100,101,104,108,109,110,117,120,128,138,150,153,155,174,180,198, C.I Pigment red 1,3,5,8,9,16,17,19,22,38,57:1,90,112,122,123,127,146,184,202,209, C.I. pigment violet 1,3,5:1,16,19,23,38, C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,16, C.I. Pigment black 1,7 etc., also can use multiple pigment and form ink composition.
These pigment optimizations are contained in the black liquid of first mode of the present invention with the scope of 0.5～8 weight %.If content is less than 0.5 weight %, then have the insufficient situation of lettering concentration (color emissivity), when greater than 8 weight %, then have the glossiness deterioration on glossy media or cause that the obstruction of nozzle, the instability of ejection etc. produce the not situation of good situation aspect reliability in addition.
In addition, from the storage stability of dispersion stabilization, black liquid or prevent the viewpoints such as obstruction of nozzle, viewpoints such as the glossiness on the glossy media are considered, the preferred tinting material of the weight ratio of tinting material and insoluble polymer: the ratio of insoluble polymer=1: 0.2～1: 1.Be because when insoluble polymer is less than 20% with respect to tinting material, then can't stably disperse specifically, produce the cohesion of tinting material, when with respect to tinting material more than 100% the time, though then the bronzing phenomenon diminishes, but color development reduces, and the gloss on the glossy media also can variation.
In addition, the viewpoint of the glossiness on color development or the glossy media is considered, the scope of the preferred 50～150nm of median size of the pigment particles in the ink composition.And their median size can be utilized Microtrac UPA150 (Microtrac corporate system) or sedimentograph LPA3100 (Da mound electronics (strain) system) etc. particle size determination obtain.
And the tinting material that is covered by insoluble polymer of first mode of the present invention also can be that tinting material is not fully covered by insoluble polymer, the shape that the tinting material of a part exposes.
[resin emulsion]
The resin emulsion of first mode of the present invention is by constituting from the resin that obtains with the monomer component that constitutes described insoluble polymer monomer component of the same race.Here, so-called " from the resin that is obtained by monomer component of the same race " is meant, identical with described insoluble polymer, constitute by the monomeric copolymer resin of monomer with hydrophobicity base and possess hydrophilic property base, contain and have the resin that alkali generates the residues of monomers of base at least.
Monomer with hydrophobicity base has: methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, the methacrylic acid cyclohexyl ester, the methacrylic acid phenylester, benzyl methacrylate, methyl acrylic esters such as methyl propenoic acid glycidyl base ester; Vinyl esters such as vinyl-acetic ester; Vinyl cyanide compound such as vinyl cyanide, methacrylonitrile class; Aromatic vinyl monomer classes such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl benzene methyl ether, vinyl naphthalene etc. can be distinguished separately and use, and perhaps also can mix more than 2 kinds and use.
As the monomer of possess hydrophilic property base, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene glycol propylene glycol monomethyl acrylate etc. are arranged, can distinguish separately and use, perhaps also can mix more than 2 kinds and use.Particularly, then can improve the glossiness of printed images by using the monomer component of formation side chains such as polyoxyethylene glycol (2～30) monomethacrylates, polyoxyethylene glycol (1～15) propylene glycol (1～15) monomethacrylates, polypropylene glycol (2～30) methacrylic ester, methoxy poly (ethylene glycol) (2～30) methacrylic ester, methoxyl group polytetramethylene glycol (2～30) methacrylic ester, methoxyl group (ethylene glycol propylene glycol copolymers) (1～30) methacrylic ester.
Monomer with salt generation base has vinylformic acid, methacrylic acid, vinylbenzene carboxylic acid, toxilic acid etc., can distinguish separately and use, and perhaps also can mix more than 2 kinds and use.
In addition, also can and be used in macromonomer or other monomers such as styrenic macromonomer that an end has polymerizable functional groups, silicon class macromonomer.
The insoluble polymer of first mode of the present invention can be by utilizing known polymerizations such as mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization, monomer copolymerization is obtained, yet special preferred solution polymerization, in polymerization, also can add known radical polymerization mixture or polymeric chain transfer agent.
By utilizing resin dissolves that polymerization obtains in organic solvent, add neutralizing agent and water and carry out dispersion treatment, from the dispersion of gained, remove organic solvent, just can be used as resin emulsion and obtain.
Tertiary amine, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia etc. such as the preferred ethamine of neutralizing agent, Trimethylamine 99, the pH of the water dispersion of gained preferred 6～10.
By and with this resin emulsion with by the tinting material of insoluble polymer covering, just can prevent increases with respect to the ratio of tinting material and the color development that produces reduces, gloss on the glossy media worsens along with insoluble polymer, in addition, along with increasing of the resinous principle in the ink composition, the rub resistance of stationarity or gloss change and so on improves.
In general, utilizing polymeric dispersant to disperse in the dispersion of tinting material, and when being used as the polymkeric substance such as resin emulsion of additive, then in as the polymkeric substance of dispersion agent and polymkeric substance as additive, can cause adsorption desorption with respect to tinting material, dispersion stabilization is damaged, the problem that has storage stability to worsen, yet, the resin of the resin emulsion of first mode of the present invention similarly constructs because of having with the insoluble polymer that is covered with toner, therefore even in ink composition, caused under the situation of adsorption desorption of resin of insoluble polymer and resin emulsion, also can keep stable dispersion state.
In addition, because of the resin of the resin emulsion of first mode of the present invention is the polymkeric substance of 1.5～4 times weight-average molecular weight for the molecular weight with respect to this insoluble polymer, thereby can provide the ink composition that stationarity is good, reliability is high.This be because, the weight-average molecular weight of this resin with respect to the molecular weight of insoluble polymer less than 1.5 times situation under, fixed action is insufficient, surpassing under 4 times the situation, can bring not good influence to spraying reliabilities such as stability.
In addition, the viewpoint of improving from the glossiness or the bronzing phenomenon of dispersion stabilization, document image considers that the median size of resin emulsion preferably is in the scope of 20～200nm.And their median size can be utilized Microtrac UPA150 (Microtrac corporate system) or sedimentograph LPA3100 (Da mound electronics (strain) system) etc. particle size determination obtain.
Below, will the ink composition based on second mode of the present invention preferred embodiment be elaborated based on it.
The ink composition of second mode of the present invention is to contain the tinting material that is covered by insoluble polymer, the ink composition of resin particle at least, it is characterized in that, insoluble polymer is the polymkeric substance that uses polymerizability unsaturated monomer and polymerization starter to utilize solution polymerization process to obtain at least, the tinting material that is covered by insoluble polymer is to utilize the following look material that emulsion process obtains that changes mutually, promptly, after being dissolved in this insoluble polymer in the organic solvent, at least add tinting material and water mixes, remove organic solvent, be scattered in the aqueous systems; Resin particle is to use polymerizability unsaturated monomer and polymerization starter at least, the polymkeric substance that utilizes emulsion polymerization to obtain.
Be elaborated for these integrants.
[tinting material]
Used tinting material in the ink composition as second mode of the present invention can use existing dyestuff, the pigment of record in " dyestuff handbook " (publisher: ball is apt to Co., Ltd.) etc.
The tinting material of the preferred water fast of tinting material of second mode of the present invention, preferred tinting material are pigment.As the pigment that can be used for second mode of the present invention, can use any kind of known mineral dye and pigment dyestuff, the pigment such as the Pigment Yellow 73 of in color table, putting down in writing, Pigment red, pigment violet, Pigment blue, Pigment black, can also pigment such as phthalocyanines, azo class, anthraquinone class, azomethine class, condensation lopps be shown example.In addition, can also enumerate yellow No. 4, No. 5, No. 205, No. 401; Orange No. 228, No. 405; Mineral dyes such as pigment dyestuff such as blue No. 1, No. 404, titanium oxide, zinc oxide, zirconium white, ferric oxide, ultramarine, Prussian blue, chromic oxide.For example, C.I. Pigment Yellow 73 1,3,12,13,14,17,24,34,35,37,42,53,55,74,81,83,95,97,98,100,101,104,108,109,110,117,120,128,138,150,153,155,174,180,198, the C.I Pigment red 1,3, and 5,8,9,16,17,19,22,38,57:1,90,112,122,123,127,146,184,202,209, C.I. pigment violet 1,3,5:1,16,19,23,38, C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,16, C.I. Pigment black 1,7 etc., also can use multiple pigment and form ink composition.
These pigment optimizations are contained in the black liquid of second mode of the present invention with the scope of 0.5～8 weight %.If content is less than 0.5 weight %, then have the insufficient situation of lettering concentration (color emissivity), when greater than 8 weight %, then have the glossiness deterioration on glossy media or cause that the obstruction of nozzle, the instability of ejection etc. produce the not situation of good situation aspect reliability in addition.
[look material :] by the tinting material of insoluble polymer covering
In the tinting material that covers by insoluble polymer of second mode of the present invention used insoluble polymer be use polymerizability unsaturated monomer and polymerization starter to utilize the solution polymerization process polymerization at least and polymkeric substance.Here, so-called insoluble polymer is meant that the solubleness of neutralization back in 25 ℃ water 100g is less than the polymkeric substance of 1g.
As the polymerizability unsaturated monomer, can enumerate vinyl aromatic hydrocarbon, methyl acrylic ester, Methacrylamide, alkyl substituent methyl acrylamide, maleic anhydride, vinyl cyanide compound class, methyl vinyl ketone, vinyl-acetic ester etc.Specifically, vinylbenzene is arranged, alpha-methyl styrene, Vinyl toluene, the 4-t-butyl styrene, chloro-styrene, the vinyl benzene methyl ether, vinyl naphthalene, methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, the methacrylic acid cyclohexyl ester, the methacrylic acid phenylester, benzyl methacrylate, methyl propenoic acid glycidyl base ester, vinyl cyanide, methacrylonitrile etc., can distinguish separately and use, perhaps also can mix more than 2 kinds and use.
In addition, in order to give the glossiness of printed images, the insoluble polymer of second mode of the present invention preferably contains the monomer of possess hydrophilic property base and has the monomer that alkali generates base as its constituent.
As the monomer of possess hydrophilic property base, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene glycol propylene glycol monomethyl acrylate etc. are arranged, can distinguish separately and use, perhaps also can mix more than 2 kinds and use.Particularly, then can improve the glossiness of printed images by using the monomer component of formation side chains such as polyoxyethylene glycol (2～30) monomethacrylates, polyoxyethylene glycol (1～15) propylene glycol (1～15) monomethacrylates, polypropylene glycol (2～30) methacrylic ester, methoxy poly (ethylene glycol) (2～30) methacrylic ester, methoxyl group polytetramethylene glycol (2～30) methacrylic ester, methoxyl group (ethylene glycol propylene glycol copolymers) (1～30) methacrylic ester.
Monomer with salt generation base has vinylformic acid, methacrylic acid, vinylbenzene carboxylic acid, toxilic acid etc., can distinguish separately and use, and perhaps also can mix more than 2 kinds and use.
In addition, also can and be used in an end and have macromonomer or other monomers such as the styrenic macromonomer of polymerizable functional groups, polysiloxane-based macromonomer.
In addition, in polymerization, also can add known radical polymerization mixture or polymeric chain transfer agent.
The tinting material that is covered by insoluble polymer used in second mode of the present invention is to utilize to change the tinting material that emulsion process obtains mutually.Promptly, described insoluble polymer is dissolved in the organic solvents such as methyl alcohol, ethanol, Virahol, propyl carbinol, acetone, methyl ethyl ketone, dibutyl ether, in the solution of gained, add tinting material, add neutralizing agent and water then and carry out dispersion mixing, that dispersion treatment is adjusted oil droplet type in the water, by from the dispersion of gained, removing organic solvent, and obtain as water dispersion.Mixing, dispersion treatment for example can be used ball mill, roller mill, ball mill, high-pressure homogenizer, high-speed stirring type dispersion machine etc.
Tertiary amine, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia etc. such as the preferred ethamine of neutralizing agent, Trimethylamine 99, the pH of the water dispersion of gained preferred 6～10.
In addition,, make tinting material as the insoluble polymer that covers, pigment dispersive aspect stably particularly, preferable weight-average molecular weight is about 10000～150000 polymkeric substance.Weight-average molecular weight can utilize the molecular weight analyse method of gel permeation chromatography (GPC) to measure.
In addition, the viewpoint of the glossiness on color development or the glossy media is considered, the scope of the preferred 50～150nm of median size in the ink composition.And their median size can be utilized MicrotracUPA150 (Microtrac corporate system) or sedimentograph LPA3100 (Da mound electronics (strain) system) etc. particle size determination obtain.
And the tinting material that is covered by insoluble polymer of second mode of the present invention also can be that tinting material is not fully covered by insoluble polymer, the shape that the tinting material of a part exposes.
[resin particle]
As the resin that forms resin particle, preferably from by acrylic resin, metha crylic resin, phenylethylene resin series, polyurethane series resin, acrylamide resin, epoxy be select the group that constitutes of resin more than a kind or 2 kinds.These resins both can be homopolymer, also can be multipolymers, no matter be that a kind of can use of single-phase structure or heterogeneous structure (core-shell-type), yet used resin were to use the resin of linking agent with internal crosslinking in second mode of the present invention.
In general, when utilizing polymeric dispersant to disperse in the dispersion of tinting material and being used as the polymkeric substance of additive, then in as the polymkeric substance of dispersion agent and polymkeric substance as additive, can cause adsorption desorption with respect to tinting material, dispersion stabilization is damaged, the problem that has storage stability to worsen.But, in second mode of the present invention, because utilization changes emulsion process mutually tinting material is covered with insoluble polymer, very stable as dispersed particle, and with the resin particle internal crosslinking, therefore exist as firm resin particle, and because of the tensio-active agent that in the resin particle that utilizes emulsion polymerization to make, contains the trace that to remove (in the letex polymerization used tensio-active agent), thereby can hinder the adsorption desorption of insoluble polymer and resin particle, just can keep dispersion stabilization thus.
In addition, used resin particle preferably can not become the polymkeric substance of membranization in second mode of the present invention under the temperature below 40 ℃.The interpolation of the resin particle of second mode of the present invention is not in order to improve the stationarity or the rub resistance of the one-tenth membranization realization that utilizes resin, but for following purpose, promptly, by at the remaining particulate in recording medium surface, improve smoothness of the surface, prevent by wiping peeling off or the gloss change of stroke tinting material that causes, by using this can be at the polymkeric substance that becomes membranization below 40 ℃, compare with the situation of the polymkeric substance that has used the one-tenth membranization, have and stop up the quite good advantages of reliability such as restorative.
The form of the emulsion (for example so-called " ACRYLIC EMULSION ") of the resin particle that used resin particle preferably obtains with the letex polymerization that utilizes unsaturated monomer at least in second mode of the present invention is matched with in the ink composition.Its reason be because, even because resin particle is directly added in the ink composition, the dispersion that also has this resin particle become inadequate situation, the therefore form of preferred emulsion in the manufacturing of black liquid.
The emulsion of resin particle (ACRYLIC EMULSION etc.) can utilize known emulsion polymerization to obtain.For example, can be by in the water that has polymerization starter and tensio-active agent, unsaturated monomer (unsaturated ethylene thiazolinyl monomer etc.) letex polymerization being obtained.
As unsaturated monomer, can enumerate generally employed acrylate monomer class, methacrylate monomer class, aromatic vinyl monomer class, vinyl ester monomers class, vinyl cyanide compound monomer class, halogenated monomer class, olefinic monomer class, diene monomers class etc. in letex polymerization.As concrete example, can enumerate methyl acrylate, ethyl propenoate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, the just own ester of vinylformic acid, 2-ethylhexyl acrylate, Octyl acrylate, decyl acrylate, dodecylacrylate, the vinylformic acid stearyl, the vinylformic acid cyclohexyl ester, phenyl acrylate, benzyl acrylate, esters of acrylic acids such as vinylformic acid glycidyl esters, methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-(ethyl hexyl) ester, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, the methacrylic acid cyclohexyl ester, the methacrylic acid phenylester, benzyl methacrylate, vinyl esters such as methyl acrylic esters such as methyl propenoic acid glycidyl base ester and vinyl-acetic ester; Vinyl cyanide compound such as vinyl cyanide, methacrylonitrile class; Halogenated monomer such as vinylidene chloride, vinylchlorid class; Aromatic vinyl monomer classes such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl benzene methyl ether, vinyl naphthalene; Olefines such as ethene, propylene; Dienes such as divinyl, chloroprene; Vinyl monomer classes such as vinyl ether, vinyl ketone, vinyl pyrrolidone; Unsaturated carboxylic acid classes such as vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid; Acrylamide, Methacrylamide, N, N '-acrylic amides such as DMAA; Hydroxyl monomer classes such as 2-hydroxyethylmethacry,ate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylic ester, 2-hydroxy propyl methacrylate etc. can also can be mixed two or more uses with they independent uses.
In addition, as linking agent, can use have more than two can the two keys of polymeric cross-linkable monomer.As the example that has more than two cross-linkable monomer that can the two keys of polymeric, can enumerate polyethyleneglycol diacrylate, triethylene glycol diacrylate, 1, the 3-butylene glycol diacrylate, 1, the 4-butylene glycol diacrylate, 1, the 6-hexanediyl ester, neopentylglycol diacrylate, 1,9-nonanediol diacrylate, polypropyleneglycol diacrylate, 2,2 '-two (4-acryloxy propoxy-phenyl) propane, 2, diacrylate ester cpds such as 2 '-two (4-acryloxy diethoxy phenyl) propane, Viscoat 295, the trimethylolethane trimethacrylate acrylate, triacrylate compounds such as tetramethylol methane triacrylate, two (trishydroxymethyl) tetraacrylate, the tetramethylol methane tetraacrylate, tetraacrylate compounds such as tetramethylol methane tetraacrylate, six acrylic compound such as dipentaerythritol acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, 1, the 6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, the dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, the polytetramethylene glycol dimethacrylate, 2, dimethacrylate compounds such as 2 '-two (4-methacryloxy diethoxy phenyl) propane, trimethylolpropane trimethacrylate, trimethacrylate compounds such as trimethylolethane trimethacrylate methacrylic ester, methylene-bisacrylamide, Vinylstyrene etc., they independent uses perhaps can be mixed two or more uses.
In addition, in letex polymerization, the used polymerization starter and tensio-active agent, also can use chain-transfer agent and neutralizing agent etc. according to well-established law.Particularly as neutralizing agent, the oxyhydroxide of preferred ammonia, mineral alkali, for example sodium hydroxide or potassium hydroxide etc.
In second mode of the present invention, consider that from the viewpoint of the suitable ink-jet physics value that more effectively obtains black liquid, reliability (stop up or ejection stability etc.), stationarity or glossiness etc. resin particle preferably is contained in the black liquid of second mode of the present invention by the scope with 0.1～5 weight %.
On the other hand, median size for resin particle used in second mode of the present invention, in order not make the dispersion stabilization in the ink composition, the glossiness of document image worsen ground, by the be improved effect of rub resistance of the slipperiness of utilizing particle to improve the recording medium surface, the preferred 20～80nm of its median size.And their median size can be utilized Microtrac UPA150 (Microtrac corporate system) or sedimentograph LPA3100 (Da mound electronics (strain) system) etc. particle size determination obtain.
[water-soluble organic compounds]
Based on the ink composition of first mode of the present invention and based on the ink composition (being designated hereinafter simply as " ink composition of the present invention " or " ink composition ") of second mode is the ink composition that is suitable for ink jet recording method, contains water and water-soluble organic compounds.Water is main solvent, preferably uses ion exchanged water, surpasses pure water or ultrapure waters such as drainage, reverse osmosis water, distilled water.Particularly consider the generation that prevents mould or bacterium and the aspect that realizes the prolonged preservation of ink composition, the preferred use utilizes uviolizing or hydrogen peroxide interpolation etc. to carry out the water of sterilising treatment.
As described water-soluble organic compounds, for example can enumerate glycerine, 1,2, the 6-hexanetriol, ethylene glycol, propylene glycol, glycol ether, triglycol, Tetraglycol 99, five glycol, dipropylene glycol, 2-butylene-1, the 4-glycol, 2-ethyl-1, the 3-hexylene glycol, 2-methyl-2, the 4-pentanediol, 1, the 2-ethohexadiol, 1, the 2-hexylene glycol, 1, the 2-pentanediol, the 4-methyl isophthalic acid, polyalcohols such as 2-pentanediol, trimethylolethane, hydroxymethyl-propane, glucose, seminose, fructose, ribose, wood sugar, pectinose, semi-lactosi, glyconic acid, sugar alcohol, (Sorbitol Powder), maltose, cellobiose, lactose, sucrose, trehalose, carbohydrates such as trisaccharide maltose, glycitols, the hyaluronic acids, the so-called solid wetting agent of urea class, ethanol, methyl alcohol, butanols, propyl alcohol, carbon numbers such as Virahol are 1～4 alkyl alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary positive propyl ether, the glycol monomethyl isopropyl ether, the diglycol monotertiary isopropyl ether, ethylene glycol mono-n-butyl ether, glycol monomethyl uncle butyl ether, diglycol monotertiary uncle butyl ether, 1-methyl isophthalic acid methoxybutanol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list uncle butyl ether, propylene glycol list positive propyl ether, propylene glycol list isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list positive propyl ether, glycol ethers such as dipropylene glycol list isopropyl ether, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolone, methane amide, ethanamide, methyl-sulphoxide, Sorbitol Powder, sorbitan, glycerol acetate, glyceryl diacetate, vanay, sulfone etc., can use they more than a kind or 2 kinds, for guaranteeing to appropriate physics value (viscosity etc.) of ink composition, to printing quality, the viewpoint of guaranteeing of reliability, these water-soluble organic compounds preferably contain 10～50 weight % in ink composition.
In addition, among the present invention,, with the butyl ethers of polyalcohols, solid wetting agent and glycol, printing quality, ejection stability just can be provided, stop up the good ink compositions of reliability such as restorative by at least also as water-soluble organic compounds.This be because, polyalcohols, solid wetting agent are suitable for the infiltrative control on the recording medium of common paper to water-retentivity (moisture retention) and ink composition, the butyl ethers of glycol is suitable for spraying stability and the infiltrative control of ink composition on recording medium, by with them and usefulness, just can provide the high ink compositions of reliability such as printing quality, ejection stability, obstruction be restorative.
As particularly preferred water-soluble organic compounds, can enumerate: polyalcohols is for being selected from glycerine, glycol ether, triglycol, 1,5-pentanediol and 1, also using more than 2 kinds in the 2-hexylene glycol, the solid wetting agent is trimethylolethane or TriMethylolPropane(TMP) or urea, and the butyl glycols is diethylene glycol monobutyl ether or triglycol monobutyl ether.
[other additive]
In addition, in order to control the wetting property of black liquid to recording medium, the glossiness of giving homogeneous obtains the perviousness on recording medium and the lettering stability of ink jet recording method, preferably contains surface tension and adjusts agent.Adjust agent as surface tension, preferred acetylenediol class tensio-active agent or polyether modified siloxane class.
As the example of acetylenediol class tensio-active agent, can enumerate Surfynol420,440,465,485,104, STG (Air Products company product), Olefine PD-001, SPC, E1004, E1010 (day letter chemical industry (strain) product), Acetyrenol E00, E40, E100, LH (FineChemical (strain) product is ground in the river) etc.In addition, as the polyether modified siloxane class, can enumerate BYK-346,347,348, UV3530 (BYK company product) etc.They also can use multiple in ink composition, preferably surface tension are adjusted into 20～40mN/m, contain 0.1～3.0 weight % in black liquid.
In addition, in ink composition of the present invention, preferably contain pH and adjust agent.
Adjust agent as pH, can use amines such as alkali-metal oxyhydroxide such as lithium hydroxide, potassium hydroxide, sodium hydroxide, ammonia, trolamine, tripropanol amine, diethanolamine, monoethanolamine etc., preferably contain at least a pH that is selected from alkali-metal oxyhydroxide, ammonia, trolamine, the tripropanol amine and adjust agent, be adjusted into pH6～10.When pH breaks away from this scope, then can cause detrimentally affect, or make and stop up restorative deterioration the material that constitutes ink jet printer etc.
In addition, as required, also can add defoamer, antioxidant, UV light absorber, Antisepticize and mildew preventive etc.
Ink composition of the present invention goes in Writing instrument class, the stamps etc. such as pen, yet more is applicable in the ink for inkjet recording liquid group.So-called ink-jet recording is meant among the present invention, with black liquid from fine nozzle as drop ejection, make this drop be attached to mode on the recording medium.Specify as follows.
As first method, static suction mode is arranged, this mode is to nozzle and places between the accelerating electrode in the place ahead of nozzle and apply highfield, from nozzle, spray black liquid continuously with droplet-like, at ink droplet during circling in the air between deflection electrode, provide the printing information signal and the mode that writes down to deflection electrode, or the mode of ink droplet deflection ground and printing information signal not being sprayed accordingly.
As second method, be black liquid to be exerted pressure with pony pump, by with vibrating nozzle mechanically such as quartz crystal, and the mode of forcibly spraying ink droplet.The ink droplet that is sprayed is charged when spraying, and, the printing information signal is provided and carries out record to deflection electrode during circling in the air between deflection electrode at ink droplet.
Third party's method is to use the mode of piezoelectric element, is to utilize piezoelectric element to exert pressure and the printing information signal mode of injection record ink droplet simultaneously to black liquid.
Cubic formula is to utilize the effect of heat energy to make the mode of black liquid volumetric expansion sharp, is with black liquid microelectrode foamable, the mode of injection record ink droplet according to the printing information signal.
Above mode arbitrarily may be used to use in the ink jet recording method of ink composition of the present invention.
Record thing of the present invention is the material that uses described ink composition to write down at least.This record thing provides and can be used as color development record thing good, that have reflecting feel because of using ink composition of the present invention, and can also be used as the good record thing of rub resistance provides.
Embodiment
Below, will use embodiment that the present invention is further elaborated, yet the present invention is not limited to these embodiment.
[embodiment 1A～5A and comparative example 1A～4A]
[adjustment of colorant dispersion]
The tinting material that utilizes following method to adjust will to be covered by insoluble polymer is as the colorant dispersion of dispersed particle.
(synthesizing of insoluble polymer 1～3)
Each monomer shown in (methyl ethyl ketone) 20 weight parts, polymeric chain transfer agent (2 mercapto ethanol) 0.03 weight part, polymerization starter, the table 1 with an organic solvent, join in the reaction vessel that has carried out nitrogen replacement fully, polymerization under 75 ℃ of stirrings, with respect to monomer component 100 weight parts, add being dissolved in 2 in methyl ethyl ketone 40 weight parts, two (2, the 4-methyl pentane nitrile) 0.9 weight parts of 2 '-azo, wore out 1 hour down at 80 ℃, obtained polymers soln.
[table 1]
| The composition of monomer mixture (weight %) | Insoluble polymer 1 | Insoluble polymer 2 | Insoluble polymer 3 |
| Methacrylic acid | 20 | 15 | 20 |
| Styrene monomer | 45 | 30 | 40 |
| Benzyl methacrylate | 20 | ||
| Polyethylene glycol monomethacrylate (EO=15) | 5 | 10 | |
| Polypropylene glycol monomethacrylate (PO=9) | 10 | 25 | |
| Polyoxyethylene glycol propylene glycol monomethyl acrylate (EO=5, PO=7) | 10 | 5 | |
| The vinylbenzene macromonomer | 20 | 15 | 10 |
| Weight-average molecular weight | 90000 | 130000 | 70000 |
(colorant dispersion 1)
The polymers soln drying under reduced pressure that will obtain as insoluble polymer 1 is dissolved in 5 parts of gained in 15 parts of the methyl ethyl ketones, uses in the aqueous sodium hydroxide solution and polymkeric substance.Then, add 15 parts of C.I. Pigment Yellow 73s 74, mixing with dispersion machine when adding water.
After stirring, under reduced pressure, remove methyl ethyl ketone at 60 ℃ add 100 parts of ion exchanged waters in the mixing thing of gained, by removing the water of a part, having obtained solid formation branch concentration is the water dispersion of the yellow ultramarine of 20 weight % then.
(colorant dispersion 2)
The polymers soln drying under reduced pressure that will obtain as insoluble polymer 2 is dissolved in 6 parts of gained in 45 parts of the methyl ethyl ketones, uses in the aqueous sodium hydroxide solution and polymkeric substance.Then, add 18 parts of C.I. pigment violet 1s 9, mixing with dispersion machine when adding water.
After stirring, under reduced pressure, remove methyl ethyl ketone at 60 ℃ add 120 parts of ion exchanged waters in the mixing thing of gained, by removing the water of a part, having obtained solid formation branch concentration is the water dispersion of the magenta pigment of 20 weight % then.
(colorant dispersion 3)
The polymers soln drying under reduced pressure that will obtain as insoluble polymer 3 is dissolved in 8 parts of gained in 15 parts of the methyl ethyl ketones, uses in the aqueous sodium hydroxide solution and polymkeric substance.Then, add 12 parts of C.I. pigment Blue 15s: 4, mixing with dispersion machine when adding water.
After stirring, under reduced pressure, remove methyl ethyl ketone in the mixing thing of gained, adding 100 parts of ion exchanged waters, then by removing the water of a part, obtained solid formation branch concentration the water dispersion that is the blue-greenish colour pigment of 20 weight % at 60 ℃.
[modulation of resin emulsion]
The polymkeric substance that constitutes resin emulsion is not to use the monomer shown in the table 1, and is to use the monomer shown in the table 2, can be with modulating with the synthetic identical method of described insoluble polymer 1～3.
Table 2
| The composition of monomer mixture (weight %) | Insoluble polymer-4 | Insoluble polymer-5 | Insoluble polymer-6 |
| Methacrylic acid | 20 | 15 | 20 |
| Styrene monomer | 40 | 30 | 42 |
| Benzyl methacrylate | 10 | ||
| Polyethylene glycol monomethacrylate (EO=15) | 15 | 20 | |
| Polypropylene glycol monomethacrylate (PO=9) | 15 | 25 | |
| Polyoxyethylene glycol propylene glycol monomethyl acrylate (EO=5, PO=7) | 15 | 3 | |
| The vinylbenzene macromonomer | 10 | 10 | 10 |
| Weight-average molecular weight | 200000 | 300000 | 85000 |
(resin emulsion 1)
The polymers soln drying under reduced pressure that will obtain as insoluble polymer 4 is dissolved in 5 parts of gained in 15 parts of the methyl ethyl ketones, uses in the aqueous sodium hydroxide solution and polymkeric substance.After in this corrective, adding 100 parts of ion exchanged waters and stirring, under reduced pressure, remove methyl ethyl ketone, remove the water of a part then, the resin emulsion 1 that to have obtained solid formation branch concentration be 15 weight % at 60 ℃.
(resin emulsion 2)
The polymers soln and the resin emulsion 1 that obtain as insoluble polymer 5 are handled in the same manner the resin emulsion 2 that to have obtained solid formation branch concentration be 15 weight %.
(resin emulsion 3)
The polymers soln and the resin emulsion 1 that obtain as insoluble polymer 6 are handled in the same manner the resin emulsion 3 that to have obtained solid formation branch concentration be 15 weight %.
[modulation of black liquid]
With the ratio shown in the table 3 each composition is mixed, at room temperature stirred 2 hours after, be the film filter filtration of 5 μ m with the aperture, modulated each black liquid.Wherein, the addition shown in the table 3 represents as weight % concentration that all the solid formation of the numeral tinting material in () of colorant dispersion divides concentration.In addition, " the residual amount " of so-called ion exchanged water is meant, adds ion exchanged water, makes black liquid total amount reach 100 parts.
Table 3
| China ink liquid is formed | Embodiment 1A | Embodiment 2A | Embodiment 3A | Embodiment 4A | Embodiment 5A | Comparative example 1A | Comparative example 2A | Comparative example 3A | Comparative example 4A | |
| Tinting material | Colorant dispersion 1 | 36(5.4) | 30(5) | 30(4.5) | ||||||
| Colorant dispersion 2 | 30(4.5) | 30(4.5) | ||||||||
| Colorant dispersion 3 | 30(3.6) | 30(3.6) | 30(3.6) | |||||||
| C.I. Pigment Yellow 73-74 (dispersion of styrene-propene acid resin) | (4.5) | |||||||||
| Resin emulsion | Resin emulsion 1 | 6 | 8 | 2 | 3 | |||||
| Resin emulsion 2 | 2 | 6 | 8 | |||||||
| Resin emulsion 3 | 8 | |||||||||
| Polyvalent alcohol | Glycerine | 10 | 10 | 15 | 12 | 10 | 10 | 15 | 15 | 12 |
| Triglycol | 5 | 5 | 2 | 5 | 5 | 5 | ||||
| 1, the 2-hexylene glycol | 1 | 1 | 2 | 1 | 2 | 2 | 1 | |||
| 1, the 5-pentanediol | 1 | 1 | ||||||||
| The solid wetting agent | TriMethylolPropane(TMP) | 2 | 2 | 4 | 2 | 2 | ||||
| Urea | 3 | 3 | 3 | |||||||
| Glycol ethers | DEGmBE | 2 | ||||||||
| TEGmBE | 2 | 2 | 2 | 3 | 2 | 2 | 2 | 2 | ||
| 2-Pyrrolidone | 1 | 2 | 2 | 2 | ||||||
| Olfine E1010 | 1 | 0.5 | 0.7 | 1.5 | 1 | 0.7 | 0.7 | 1 | ||
| Surfynol 104 | 0.5 | 0.3 | 0.7 | 1 | 0.5 | 0.7 | 0.7 | 0.5 | ||
| Trolamine | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
| EDTA | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
| Proxel XL2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| Ion exchanged water | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | |
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
EDTA: disodium ethylene diamine tetraacetate
(test 1) median size
Use particles distribution instrument (UPA-150 of Microtrac corporate system), each ink composition is diluted 1000 times with pure water, measure the size-grade distribution of diluent, try to achieve volume average particle size.
(test 2) bronzing phenomenon
For each ink composition, use ink jet printer PX-V600, make 100% and the speckle pattern (patch pattern) of 50%Duty, at the EPSON photo with paper＜gloss (trade(brand)name: Seiko Epson Corp's system) the exploring degree of going up with 1440dpi prints, under luminescent lamp (F11 light source), change the angle of print and observe, catoptrical tonal variation is judged based on following benchmark with visual.
A: the reflected light of any speckle all is a white, can observe the tone that does not have the difference sense
B:, can observe the tone that does not have the difference sense though in the speckle of certain, can in reflected light, slightly see color
C: can in the reflected light of print, see color, variant sense.
(test 3) glossiness
For the print of test 2, use glossometer GM-268 (Konica Minolta corporate system) to measure 20 ° of gloss (G
20), the result according to the mean value of glossiness judges based on following benchmark.And, demonstrate high value even find in general as 60 ° of gloss that the index of the specular gloss of print is used, glossiness is also inconsistent with the reflecting feel of appearance, the result of further investigation is, owing to distinguish that the glossiness of 20 ° of angle of visibilities is consistent with the reflecting feel of appearance, thus in the present invention with the gloss of 20 ° of angle of visibilities as desired value.
A：60≤G
20
B：45≤G
20＜60
C：G
20＜45
(test 4) stationarity
Print for test 2, after printing, will write down the thing seasoning after 24 hours, use a yellow aqueous fluorescent ZEBRA PEN2 (registered trademark) of Zebra corporate system, pressure with 300g/15mm is wiped the brush literal that prints, and has utilized visual observation dirty having or not.Judged its result based on following benchmark.
A: also do not produce dirty fully 2 times even will wipe to draw with a part.
B:, in 2 times wiping is drawn, produce dirty though in 1 time wiping is drawn, do not produce dirtyly.
C: in 1 time wiping is drawn, produce dirty.
(test 5) gloss changes
For test 2 print, after printing, will write down the thing seasoning after about 2 hours, wipe lightly stroke with finger, utilize visual observation the chatoyant of printing surface have or not.Judged its result based on following benchmark.
A: can't discern with finger and wipe the vestige of drawing, lackluster variation
B: wipe the vestige of drawing, lackluster basically variation though can slightly discern with finger
C: can discern with finger and wipe the vestige of drawing
(test 6) storage stability
Under the state of aluminum bag that 50g China ink liquid has been packed into, under 70 ℃ environment, placed for 1 week.After the placement,, in addition,, and, judge based on following benchmark for the variation of rerum natura (viscosity, surface tension, pH, particle dia) for the sample that does not have production of foreign matters for the generation that has or not foreign matter (sediment).
A: do not have production of foreign matters, also do not have the variation of rerum natura.
B: though there is not production of foreign matters, rerum natura slightly changes.
C: there is foreign matter to produce, or the rerum natura considerable change.
(test 7) ejection stability
Lettering in testing the printing 2 is begun to use up leak source or flight bending that whether black liquid has taken place to black liquid to be estimated, in addition under situation about having taken place, needs are estimated as the type printer cleaning of carrying out to the restoring action of normal printing several times, judged based on following benchmark.
A: do not take place or clean 1 time.
B: clean 2 or 4 times.
C: cleaning is more than 5 times.
(test 8) stops up restorative
Use ink jet printer PX-V600, each black liquid is filled in the shower nozzle, affirmation sprays black liquid from whole nozzles after, do not having under the state of print cartridge, and (shower nozzle departs from the position of being located at the cap on the type printer to the position outside original position (home position), the state that on shower nozzle, does not add cap), under 40 ℃ environment, placed for 1 week.After the placement, investigated the number of times of needed cleaning before from whole nozzles, spraying ink composition once more, judged based on following benchmark.
A: clean 1 time.
B: clean 2～5 times.
C: cleaning is more than 6 times
Above evaluation result is summarised in the table 4.
Table 4
| Embodiment 1A | Embodiment 2A | Embodiment 3A | Embodiment 4A | Embodiment 5A | Comparative example 1A | Comparative example 2A | Comparative example 3A | Comparative example 4A | |
| Test 1 | 100nm | 120nm | 90nm | 120nm | 100nm | 100nm | 90nm | 90nm | 160nm |
| Test 2 | A | A | A | A | A | C | A | A | C |
| Test 3 | A | A | A | A | A | A | A | A | C |
| Test 4 | A | A | A | A | A | B | A | B | C |
| Test 5 | A | A | A | A | A | C | A | C | C |
| Test 6 | A | A | A | A | A | A | A | A | B |
| Test 7 | A | A | A | A | A | A | C | A | C |
| Test 8 | A | A | A | A | A | A | B | C | C |
From table 4, be clear that, according to ink composition of the present invention, be can be on various recording mediums, particularly have the ink composition of the image that obtains to have good reflecting feel on the glossy recording medium, the bronzing phenomenon is few, and rub resistances such as stationarity or gloss change are also good.In addition, storage stability is good, ejection stability or stop up restorative well, and the reliability height is the black liquid group that is applicable to ink-jet recording.
[embodiment 1B～5B and comparative example 1B～2B]
[colorant dispersion]
Used synthetic colorant dispersion 1～3 among the described embodiment.
[modulation of resin particle]
Utilize following method to modulate with the resin dispersion liquid (emulsion) of resin particle as dispersed particle.And becoming having or not of membranization is in the environment of about 25 ℃ indoor surrounding temperature, is coated with emulsion on aluminium sheet thinly, utilizes visual judgement.In addition, particle dia is a value of utilizing the median size that the particle size distribution of Microtrac UPA150 (Microtrac corporate system) obtains.
(manufacturing process of resin particle 1)
In the reaction vessel that has possessed stirrer, reflux exchanger, dropper and thermometer, add ion exchanged water 1000g and Sodium Lauryl Sulphate BP/USP 6.5g, be warming up to 70 ℃ when under agitation carrying out nitrogen replacement.Interior temperature is remained on 70 ℃, add Potassium Persulphate 4g as polymerization starter, after the dissolving, the emulsification of in reaction soln, making in advance as followsly of dropping in 4 hours continuously, that is, in ion exchanged water 450g, Sodium Lauryl Sulphate BP/USP 2g, under agitation add acrylamide 20g, vinylbenzene 550g, butyl acrylate 200g and methacrylic acid 30g, triethylene glycol diacrylate 1g.After dropping liquid finishes, carried out 3 hours aging.
After the water-based emulsion of gained is cooled to normal temperature, add ion exchanged water and ammoniacal liquor, be adjusted into solid formation and be divided into 37 weight %, pH is 8.
The water-based emulsion of confirming gained does not become membranization under 40 ℃ temperature, the median size of resin particle is 40nm.
(manufacturing process of resin particle 2)
In the reaction vessel that has possessed stirrer, reflux exchanger, dropper and thermometer, add ion exchanged water 800g and Sodium Lauryl Sulphate BP/USP 1g, be warming up to 75 ℃ when under agitation carrying out nitrogen replacement.Interior temperature is remained on 75 ℃, add Potassium Persulphate 6g as polymerization starter, after the dissolving, the emulsification of in reaction soln, making in advance as followsly of dropping in 5 hours continuously, that is, in ion exchanged water 450g, Sodium Lauryl Sulphate BP/USP 2g, under agitation add acrylamide 20g, methyl methacrylate 600g, butyl acrylate 215g, methacrylic acid 30g, triethylene glycol diacrylate 5g.After dropping liquid finishes, carried out 3 hours aging.After the water-based emulsion of gained is cooled to normal temperature, add ion exchanged water and aqueous sodium hydroxide solution, be adjusted into solid formation and be divided into 40 weight %, pH is 8.
The water-based emulsion of confirming gained does not become membranization under 40 ℃ temperature, the median size of resin particle is 60nm.
(manufacturing process of resin particle 3)
In the reaction vessel that has possessed stirrer, reflux exchanger, dropper and thermometer, add ion exchanged water 900g and Sodium Lauryl Sulphate BP/USP 3g, be warming up to 70 ℃ when under agitation carrying out nitrogen replacement.Interior temperature is remained on 70 ℃, add Potassium Persulphate 4g as polymerization starter, after the dissolving, the emulsification of in reaction soln, making in advance as followsly of dropping in 4 hours continuously, that is, in ion exchanged water 450g, Sodium Lauryl Sulphate BP/USP 3g, under agitation add acrylamide 20g, vinylbenzene 300g, butyl acrylate 640g, methacrylic acid 30g and triethylene glycol diacrylate 5g.After dropping liquid finishes, carried out 3 hours aging.After the water-based emulsion of gained is cooled to normal temperature, add ion exchanged water and 5% aqueous sodium hydroxide solution, be adjusted into solid formation and be divided into 40 weight %, pH is 8.
The water-based emulsion of confirming gained does not become membranization under 40 ℃ indoor surrounding temperature, the median size of resin particle is 90nm.
(manufacturing process of resin particle 4)
In the reaction vessel that has possessed stirrer, reflux exchanger, dropper and thermometer, add ion exchanged water 800g and Sodium Lauryl Sulphate BP/USP 1g, be warming up to 75 ℃ when under agitation carrying out nitrogen replacement.Interior temperature is remained on 75 ℃, add Potassium Persulphate 6g as polymerization starter, after the dissolving, the emulsification of in reaction soln, making in advance as followsly of dropping in 5 hours continuously, that is, in ion exchanged water 450g, Sodium Lauryl Sulphate BP/USP 2g, under agitation add acrylamide 20g, methyl methacrylate 600g, butyl acrylate 215g and methacrylic acid 30g.After dropping liquid finishes, carried out 3 hours aging.After the water-based emulsion of gained is cooled to normal temperature, add ion exchanged water and aqueous sodium hydroxide solution, be adjusted into solid formation and be divided into 40 weight %, pH is 8.The water-based emulsion of confirming gained does not become membranization under 40 ℃ temperature, the median size of resin particle is 70nm.
[modulation of black liquid]
With the ratio shown in the table 5 each composition is mixed, at room temperature stirred 2 hours after, be the membrane filter filtration of 5 μ m with the aperture, modulated each black liquid.Wherein, the addition shown in the table 5 represents as weight % concentration that all the solid formation of the numeral tinting material in () of colorant dispersion divides concentration.In addition, " the residual amount " of so-called ion exchanged water is meant, adds ion exchanged water, makes black liquid total amount reach 100 parts.
Table 5
| China ink liquid is formed | Embodiment 1B | Embodiment 2B | Embodiment 3B | Embodiment 4B | Embodiment 5B | Comparative example 1B | Comparative example 2B | |
| Tinting material | Colorant dispersion 1 | 36(5.4) | 30(5) | 30(4.5) | ||||
| Colorant dispersion 2 | 30(4.5) | 30(4.5) | ||||||
| Colorant dispersion 3 | 20(3) | |||||||
| C.I. Pigment Yellow 73-74 (dispersion of styrene-propene acid resin) | (4.5) | |||||||
| Resin particle (emulsion) | Resin particle 1 | 3 | 3 | 3 | ||||
| Resin particle 2 | 2.5 | |||||||
| Resin particle 3 | 2.5 | |||||||
| Resin particle 4 | 4 | |||||||
| Polyvalent alcohol | Glycerine | 10 | 10 | 15 | 12 | 10 | 10 | 12 |
| Triglycol | 5 | 5 | 2 | 5 | 5 | 5 | ||
| 1, the 2-hexylene glycol | 1 | 1 | 2 | 1 | 1 | |||
| 1, the 5-pentanediol | 1 | 1 | ||||||
| The solid wetting agent | TriMethylolPropane(TMP) | 2 | 2 | 4 | 2 | 2 | ||
| Urea | 3 | |||||||
| Glycol ether | DEGmBE | 2 | ||||||
| TEGmBE | 2 | 2 | 2 | 3 | 2 | 2 | ||
| 2-Pyrrolidone | 1 | 2 | ||||||
| Olfine E1010 | 1 | 0.5 | 0.7 | 1.5 | 1 | 1 | ||
| Surfynol 104 | 0.5 | 0.3 | 0.7 | 1 | 0.5 | 0.5 | ||
| Trolamine | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
| EDTA | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
| Proxel XL2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| Ion exchanged water | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | Residual amount | |
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
EDTA: disodium ethylene diamine tetraacetate
Utilize and the identical method of the test 1～8 of embodiment 1A～5A and comparative example 1A～4A enforcement has been estimated these ink compositions.Evaluation result is summarised in the table 6.
Table 6
| Embodiment 1B | Embodiment 2B | Embodiment 3B | Embodiment 4B | Embodiment 5B | Comparative example 1B | Comparative example 2B | |
| Test 1 | 100nm | 120nm | 80nm | 120nm | 100nm | 100nm | 160nm |
| Test 2 | A | A | A | B | A | C | C |
| Test 3 | A | A | A | B | A | A | C |
| Test 4 | A | A | A | A | A | B | C |
| Test 5 | A | A | A | B | A | C | C |
| Test 6 | A | A | A | A | A | A | B |
| Test 7 | A | A | A | A | A | A | C |
| Test 8 | A | A | A | A | A | A | C |
From table 6, be clear that, according to ink composition of the present invention, be can be on various recording mediums, particularly have the ink composition of the image that obtains to have good reflecting feel on the glossy recording medium, the bronzing phenomenon is few, and rub resistances such as stationarity or gloss change are also good.In addition, storage stability is good, ejection stability or stop up restorative well, and the reliability height is the black liquid group that is applicable to ink-jet recording.
Though to the present invention at length, with reference to specific embodiment be illustrated, for those skilled in the art it is clear that to apply various changes or correction with not breaking away from the spirit and scope of the present invention.
The application is based on the Japanese patent application 2005-090808 of application on March 28th, 2005 and the application of 2005-090809, and its content is here added as reference.
The present invention is not limited to described embodiment, can also be applicable to that used for note writing utensil China ink liquid, offset printing are with in the purposes such as black liquid.
Claims (23)
1. ink composition, it is characterized in that, at least contain as the tinting material that covers by insoluble polymer of look material with as the resin emulsion of additive, wherein the weight-average molecular weight of insoluble polymer is 50000～150000, resin emulsion is by forming with the monomer component that constitutes this insoluble polymer monomer component of the same race, and this resin emulsion is the resin formation of 1.5～4 times weight-average molecular weight with respect to this insoluble polymer by its molecular weight.
2. ink composition according to claim 1 is characterized in that, described tinting material is water-fast tinting material.
3. ink composition according to claim 1 and 2 is characterized in that, the polymkeric substance of described insoluble polymer and formation resin emulsion is the branched chain type polymkeric substance.
4. according to any described ink composition in the claim 1～3, it is characterized in that the median size of described resin emulsion is 20～200nm.
5. according to any described ink composition in the claim 1～4, it is characterized in that, described tinting material is a pigment, and described ink composition also contains water and water-soluble organic compounds, and the median size of the pigment particles in the ink composition is in the scope of 50～150nm.
6. ink composition according to claim 5 is characterized in that, described water-soluble organic compounds is made of the butyl ethers of polyalcohols, solid wetting agent and glycol at least.
7. ink composition according to claim 6, it is characterized in that, polyalcohols is by being selected from glycerine, glycol ether, triglycol, 1,5-pentanediol and 1, constituting more than 2 kinds in the 2-hexylene glycol, the solid wetting agent is trimethylolethane or TriMethylolPropane(TMP) or urea, and the butyl glycols is diethylene glycol monobutyl ether or triglycol monobutyl ether.
8. according to any described ink composition in the claim 1～7, it is characterized in that, be used in the ink-jet recording.
9. recording method comprises any described ink composition in the claim 1～8 is attached to the operation of carrying out lettering on the recording medium.
10. recording method according to claim 9 is characterized in that, also comprises the operation of the drop that sprays black liquid, this drop is attached to carries out lettering on the recording medium.
11. a record thing is to utilize the recording method record described in claim 9 or 10.
12. ink composition, it is characterized in that, at least contain the tinting material, the resin particle that cover by insoluble polymer, wherein insoluble polymer is to use polymerizability unsaturated monomer and polymerization starter at least, the polymkeric substance that utilizes solution polymerization process to obtain, the tinting material that is covered by insoluble polymer is to utilize the following look material that emulsion process obtains that changes mutually, promptly after being dissolved in this insoluble polymer in the organic solvent, at least add tinting material and water mixes, remove organic solvent, be scattered in the emulsion process of transformation mutually in the aqueous systems; Resin particle is to use linking agent at least, the polymkeric substance that utilizes the polymerization of emulsion polymerization to obtain.
13. ink composition according to claim 12 is characterized in that, described tinting material is water-fast tinting material.
14., it is characterized in that described insoluble polymer is the branched chain type polymkeric substance according to claim 12 or 13 described ink compositions.
15., it is characterized in that described resin particle is by not becoming the polymkeric substance of membranization to constitute according to any described ink composition in the claim 12～14 under the temperature below 40 ℃.
16., it is characterized in that the median size of described resin particle is 20～80nm according to any described ink composition in the claim 12～15.
17. according to any described ink composition in the claim 12～16, it is characterized in that, described tinting material is a pigment, and described ink composition also contains water and water-soluble organic compounds, and the median size of the pigment particles in the ink composition is in the scope of 50～150nm.
18. ink composition according to claim 17 is characterized in that, described water-soluble organic compounds comprises the butyl ethers of polyalcohols, solid wetting agent and glycol at least.
19. ink composition according to claim 18, it is characterized in that, polyalcohols is by being selected from glycerine, glycol ether, triglycol, 1,5-pentanediol and 1, constituting more than 2 kinds in the 2-hexylene glycol, the solid wetting agent is trimethylolethane or TriMethylolPropane(TMP) or urea, and the butyl glycols is diethylene glycol monobutyl ether or triglycol monobutyl ether.
20. according to any described ink composition in the claim 12～19, it is characterized in that, be used in the ink-jet recording.
21. a recording method comprises any described ink composition in the claim 12～20 is attached to the operation of carrying out lettering on the recording medium.
22. recording method according to claim 21 is characterized in that, also comprises the operation of the drop that sprays black liquid, this drop is attached to carries out lettering on the recording medium.
23. a record thing is to utilize the recording method record described in claim 21 or 22.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005090809A JP2006273892A (en) | 2005-03-28 | 2005-03-28 | Ink composition, recording method and recorded material using the same |
| JP090808/2005 | 2005-03-28 | ||
| JP2005090808A JP2006273891A (en) | 2005-03-28 | 2005-03-28 | Ink composition, recording method and recorded material using the same |
| JP090809/2005 | 2005-03-28 | ||
| PCT/JP2006/306321 WO2006104157A1 (en) | 2005-03-28 | 2006-03-28 | Ink composition, recording method using the same, and recorded matter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101151334A true CN101151334A (en) | 2008-03-26 |
| CN101151334B CN101151334B (en) | 2011-12-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680010248XA Expired - Fee Related CN101151334B (en) | 2005-03-28 | 2006-03-28 | Ink composition, recording method using the same, and recorded matter |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006273891A (en) |
| CN (1) | CN101151334B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110770308A (en) * | 2017-06-28 | 2020-02-07 | 株式会社理光 | Ink, ink set, ink container, image forming method, and image forming apparatus |
| CN110799605A (en) * | 2017-07-03 | 2020-02-14 | 花王株式会社 | Water-based ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007021870A1 (en) * | 2007-05-10 | 2008-11-20 | Clariant International Limited | Aqueous pigment preparations |
| JP5247180B2 (en) | 2008-02-13 | 2013-07-24 | 富士フイルム株式会社 | Water-based ink for inkjet recording and method for producing the same |
| JP2009191133A (en) | 2008-02-13 | 2009-08-27 | Fujifilm Corp | Aqueous inkjet recording ink |
| JP5489473B2 (en) * | 2008-02-13 | 2014-05-14 | 富士フイルム株式会社 | Inkjet recording liquid and inkjet recording method |
| JP4668305B2 (en) | 2008-02-29 | 2011-04-13 | 富士フイルム株式会社 | Water-based colorant dispersion, method for producing water-based colorant dispersion, and water-based ink for inkjet recording |
| JP5247191B2 (en) | 2008-03-13 | 2013-07-24 | 富士フイルム株式会社 | Ink composition and image recording method |
| JP5398401B2 (en) * | 2008-08-14 | 2014-01-29 | 富士フイルム株式会社 | Ink set and image forming method |
| JP2010070669A (en) * | 2008-09-19 | 2010-04-02 | Fujifilm Corp | Inkjet recording liquid |
| JP5554035B2 (en) * | 2009-09-02 | 2014-07-23 | 富士フイルム株式会社 | Ink set and image forming method |
| JP5289252B2 (en) * | 2009-09-11 | 2013-09-11 | 富士フイルム株式会社 | Ink set and image forming method |
| JP5579460B2 (en) | 2010-02-10 | 2014-08-27 | 富士フイルム株式会社 | Ink composition and image forming method |
| JP5804724B2 (en) * | 2011-02-22 | 2015-11-04 | 京セラドキュメントソリューションズ株式会社 | Ink for inkjet recording apparatus |
| JP5694826B2 (en) | 2011-03-29 | 2015-04-01 | 富士フイルム株式会社 | Black ink composition, ink set, and image forming method |
| JP2015067802A (en) | 2013-09-30 | 2015-04-13 | 富士フイルム株式会社 | Ink for inkjet recording, ink set, image forming method, and maintenance method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259871A (en) * | 1995-03-28 | 1996-10-08 | Toyobo Co Ltd | Aqueous dispersion containing colored fine particle |
| JP4221626B2 (en) * | 1998-06-18 | 2009-02-12 | Ｄｉｃ株式会社 | Water-based ink composition |
| JP3552165B2 (en) * | 2001-01-29 | 2004-08-11 | セイコーエプソン株式会社 | Recording method for printing on a recording medium using two liquids |
| JP2001123098A (en) * | 1999-08-19 | 2001-05-08 | Seiko Epson Corp | Ink composition for ink jet recording |
| JP2004091627A (en) * | 2002-08-30 | 2004-03-25 | Mitsubishi Paper Mills Ltd | Water-based pigment ink for ink-jet printing use |
| JP2004204079A (en) * | 2002-12-25 | 2004-07-22 | Seiko Epson Corp | Ink composition, method for recording with the composition, and recording formed by the method |
-
2005
- 2005-03-28 JP JP2005090808A patent/JP2006273891A/en not_active Withdrawn
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110770308A (en) * | 2017-06-28 | 2020-02-07 | 株式会社理光 | Ink, ink set, ink container, image forming method, and image forming apparatus |
| US11499062B2 (en) | 2017-06-28 | 2022-11-15 | Ricoh Company, Ltd. | Ink, ink set, ink container, image forming method, and image forming apparatus |
| CN110799605A (en) * | 2017-07-03 | 2020-02-14 | 花王株式会社 | Water-based ink |
| US11180671B2 (en) | 2017-07-03 | 2021-11-23 | Kao Corporation | Aqueous ink |
| US11773278B2 (en) | 2017-07-03 | 2023-10-03 | Kao Corporation | Aqueous ink |
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| CN101151334B (en) | 2011-12-21 |
| JP2006273891A (en) | 2006-10-12 |
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